Titanium and titanium alloys

ABSTRACT

A titanium powder or alloy powder produced by introducing a TiCl 4  vapor into a continuum or flowing stream of sodium metal at a velocity not less than sonic velocity of the vapor wherein the sodium is present in an amount greater than stoichiometric sufficient to maintain substantially all the reaction products below the sintering temperature thereof and wherein said Ti powder has a packing fraction in the range of from about 4% to about 11%. The powders without fines have a particle diameter in the range of from about 3.3 to about 1.3 microns based on a calculated size of a sphere from a BET surface area in the range of from about 0.4 to about 1.0 m 2 /g.

RELATED APPLICATIONS

This application is a continuation of Ser. No. 08/691,423 filed Aug. 2,1995, now U.S. Pat. No. 5,797,761 and this application is a continuationof the file wrapper continuation application of our previously filedco-pending application Ser. No. 09/264,577 filed Mar. 8, 1999, now U.S.Pat. No. 6,409,979 issued Jul. 25, 2002, which was acontinuation-in-part of Ser. No. 08/782,816, filed Jan. 13, 1997, nowU.S. Pat. No. 5,958,106 issued Sep. 28, 1999, which was acontinuation-in-part of Ser. No. 08/691,423, filed Aug. 2, 1995, nowU.S. Pat. No. 5,779,761 issued Jul. 14, 1998. The disclosures of each ofU.S. Pat. Nos. 5,779,761 and 5,958,106 are incorporated by reference.

BACKGROUND OF THE INVENTION

This invention relates to the production of elemental material from thehalides thereof and has particular applicability to those metals andnon-metals for which the reduction of the halide to the element isexothermic. Particular interest exists for titanium and the presentinvention will be described with particular reference to titanium, butis applicable to other metals and non-metals such as Al, As, Sb, Sn, Be,B, Ta, Ge, V, Nb, Mo, Ga, Ir, Os, U and Re, all of which producesignificant heat upon reduction from the halide to the metal. For thepurposes of this application, elemental materials include those metalsand non-metals listed above or in Table 1.

At present titanium production is by reduction of titaniumtetrachloride, which is made by chlorinating relatively high-gradetitanium dioxide ore. Ores containing rutile can be physicallyconcentrated to produce a satisfactory chlorination feed material; othersources of titanium dioxide, such as ilmenite, titaniferous iron oresand most other titanium source materials, require chemicalbeneficiation.

The reduction of titanium tetrachloride to metal has been attemptedusing a number of reducing agents including hydrogen, carbon, sodium,calcium, aluminum and magnesium. Both the magnesium and sodium reductionof titanium tetrachloride have proved to be commercial methods forproducing titanium metal. However, current commercial methods use batchprocessing which requires significant material handling with resultingopportunities for contamination and gives quality variation from batchto batch. The greatest potential for decreasing production cost is thedevelopment of a continuous reduction process with attendant reductionin material handling. There is a strong demand for both the developmentof a process that enables continuous economical production of titaniummetal and for the production of metal powder suitable for use withoutadditional processing for application to powder metallurgy or forvacuum-arc melting to ingot form.

The Kroll process and the Hunter process are the two present day methodsof producing titanium commercially. In the Kroll process, titaniumtetrachloride is chemically reduced by magnesium at about 1000° C. Theprocess is conducted in a batch fashion in a metal retort with an inertatmosphere, either helium or argon. Magnesium is charged into the vesseland heated to prepare a molten magnesium bath. Liquid titaniumtetrachloride at room temperature is dispersed dropwise above the moltenmagnesium bath. The liquid titanium tetrachloride vaporizes in thegaseous zone above the molten magnesium bath. A reaction occurs on themolten magnesium surface to form titanium and magnesium chloride. TheHunter process is similar to the Kroll process, but uses sodium insteadof magnesium to reduce the titanium tetrachloride to titanium metal andproduces sodium chloride as a by product.

For both processes, the reaction is uncontrolled and sporadic andpromotes the growth of dendritic titanium metal. The titanium fuses intoa mass that encapsulates some of the molten magnesium (or sodium)chloride. This fused mass is called titanium sponge. After cooling ofthe metal retort, the solidified titanium sponge metal is broken up,crushed, purified and then dried in a stream of hot nitrogen. Metalingots are made by compacting the sponge, welding pieces into anelectrode and then melting it into an ingot in a high vacuum arcfurnace. High purity ingots require multiple arc melting operations.Powder titanium is usually produced from the sponge through grinding,shot casting or centrifugal processes. A common technique is to firstreact the titanium with hydrogen to make brittle titanium hydride tofacilitate the grinding process. After formation of the powder titaniumhydride, the particles are dehydrogenated to produce a usable metalpowder product. The processing of the titanium sponge into a usable formis difficult, labor intensive, and increases the product cost by afactor of two to three.

The processes discussed above have several intrinsic problems thatcontribute heavily to the high cost of titanium production. Batchprocess production is inherently capital and labor intensive. Titaniumsponge requires substantial additional processing to produce titanium ina usable form; thereby increasing cost, increasing hazard to workers andexacerbating batch quality control difficulties. Neither processutilizes the large exothermic energy reaction, requiring substantialenergy input for titanium production (approximately 6 kW-hr/kg productmetal). In addition, the processes generate significant productionwastes that are of environmental concern.

SUMMARY OF THE INVENTION

Accordingly, an object of the present invention is to provide a methodand system for producing non-metals or metals or alloys thereof which iscontinuous having significant capital and operating costs advantagesover existing batch technologies.

Another object of the present invention is to provide an improved batchor semi-batch process for producing non-metals or metals or alloysthereof where continuous operations are not warranted by the scale ofthe production.

Another object of the present invention is to provide a method andsystem for producing metals and non-metals from the exothermic reductionof the halide while preventing the metal or non-metal from sinteringinto large masses or onto the apparatus used to produce same.

Still another object of the invention is to provide a method and systemfor producing non-metal or metal from the halides thereof wherein theprocess and system recycles the reducing agent and removes the heat ofreaction for use as process heat or for power generation, therebysubstantially reducing the environmental impact of the process.

The invention consists of certain novel features and a combination ofparts hereinafter fully described, illustrated in the accompanyingdrawings, and particularly pointed out in the appended claims, it beingunderstood that various changes in the details may be made withoutdeparting from the spirit, or sacrificing any of the advantages of thepresent invention.

BRIEF DESCRIPTION OF THE DRAWINGS

For the purpose of facilitating an understanding of the invention, thereis illustrated in the accompanying drawings a preferred embodimentthereof, from an inspection of which, when considered in connection withthe following description, the invention, its construction andoperation, and many of its advantages should be readily understood andappreciated.

FIG. 1 is a process flow diagram showing the continuous process forproducing as an example titanium metal from titanium tetrachloride;

FIG. 2 is an example of a burner reaction chamber for a continuousprocess;

FIG. 3 is a process diagram of a batch process reaction; and

FIG. 4 is a diagram of the apparatus used to produce titanium.

FIG. 5 is a SEM of Ti powder made by the process of the '761 and '106patents;

FIG. 6 is a SEM of Ti powder made in accordance with the process setforth in the '761 and '106 patents;

FIG. 7 is a SEM of a Ti alloy made in accordance with the process setforth in the '761 and '106 patents; and

FIG. 8 is a SEM of a Ti alloy made in accordance with the process setforth in the '761 and '106 patents.

DETAILED DESCRIPTION OF THE INVENTION

The process of the invention may be practiced with the use of any alkalior alkaline earth metal depending upon the metal or non-metal to bereduced. In some cases, combinations of an alkali or alkaline earthmetals may be used. Moreover, any halide or combinations of halides maybe used with the present invention although in most circumstanceschlorine, being the cheapest and most readily available, is preferred.Of the alkali or alkaline earth metals, by way of example, sodium willbe chosen not for purposes of limitation but merely purposes ofillustration, because it is cheapest and preferred, as has chlorine beenchosen for the same purpose.

Regarding the non-metals or metals to be reduced, it is possible toreduce a single metal such as titanium or tantalum or zirconium,selected from the list set forth hereafter. It is also possible to makealloys of a predetermined composition by providing mixed metal halidesat the beginning of the process in the required molecular ratio. By wayof example, Table 1 sets forth heats of reaction per gram of liquidsodium for the reduction of a stoichiometric amount of a vapor of anon-metal or metal halides applicable to the inventive process.

TABLE 1 FEEDSTOCK HEAT kJ/g TiCl₄ 10 AlCL₃ 9 SnCl₂ 4 SbCl₃ 14 BeCl₂ 10BCl₃ 12 TaCl₅ 11 ZrCl₄ 9 VCl₄ 12 NbCl₅ 12 MoCl₄ 14 GaCl₃ 11 UF₆ 10 ReF₆17The process will be illustrated, again for purposes of illustration andnot for limitation, with a single metal titanium being produced from thetetrachloride.

A summary process flowsheet is shown in FIG. 1. Sodium and titaniumtetrachloride are combined in a reaction chamber 14 where titaniumtetrachloride vapor from a source thereof in the form of a boiler 22 isinjected within a flowing sodium stream from a continuously cycling loopthereof including a sodium pump 11. The sodium stream is replenished bysodium provided by an electrolytic cell 16. The reduction reaction ishighly exothermic, forming molten reaction products of titanium andsodium chloride. The molten reaction products are quenched in the bulksodium stream. Particle sizes and reaction rates are controlled bymetering of the titanium tetrachloride vapor flowrate (by controllingthe supply pressure), dilution of the titanium tetrachloride vapor withan inert gas, such as He or Ar, and the sodium flow characteristics andmixing parameters in the reaction chamber which includes a nozzle forthe titanium tetrachloride and a surrounding conduit for the liquidsodium. The vapor is intimately mixed with the liquid in a zone enclosedby the liquid, i.e., a liquid continuum, and the resultant temperature,significantly affected by the heat of reaction, is controlled by thequantity of flowing sodium and maintained below the sinteringtemperature of the produced metal, such as for titanium at about 1000°C. Preferably, the temperature of the sodium away from the location ofhalide introduction is maintained in the range of from about 200° C. toabout 600° C. Products leaving the reaction zone are quenched in thesurrounding liquid before contact with the walls of the reaction chamberand preferably before contact with other product particles. Thisprecludes sintering and wall erosion.

The surrounding sodium stream then carries the titanium and sodiumchloride reaction products away from the reaction region. These reactionproducts are removed from the bulk sodium stream by conventionalseparators 15 such as cyclones, particulate filters, magnetic separatorsor vacuum stills.

Three separate options for separation of the titanium and the sodiumchloride exist. The first option removes the titanium and sodiumchloride products in separate steps. This is accomplished by maintainingthe bulk stream temperature such that the titanium is solid but thesodium chloride is molten through control of the ratio of titaniumtetrachloride and sodium flowrates to the reaction chamber 14. For thisoption, the titanium is removed first, the bulk stream cooled tosolidify the sodium chloride, then the sodium chloride is removed fromseparator

In the second option for reaction product removal, a lower ratio oftitanium tetrachloride to sodium flowrate would be maintained in thereaction chamber 14 so that the bulk sodium temperature would remainbelow the sodium chloride solidification temperature. For this option,titanium and sodium chloride would be removed simultaneously usingconventional separators. The sodium chloride and any residual sodiumpresent on the particles would then be removed in a water-alcohol wash.

In the third, and preferred option for product removal, the solid cakeof salt, Ti and Na is vacuum distilled to remove the Na. Thereafter, theTi particles are passivated by passing a gas containing some O₂ over themixture of salt and Ti followed by a water wash to remove the saltleaving Ti particles with surfaces of TiO₂, which can be removed byconventional methods.

Following separation, the sodium chloride is then recycled to theelectrolytic cell 16 to be regenerated. The sodium is returned to thebulk process stream for introduction to reaction chamber 14 and thechlorine is used in the ore chlorinator 17. It is important to note thatwhile both electrolysis of sodium chloride and subsequent orechlorination will be performed using technology well known in the art,such integration and recycle of the reaction by-product directly intothe process is not possible with the Kroll or Hunter process because ofthe batch nature of those processes and the production of titaniumsponge as an intermediate product. In addition, excess process heat isremoved in heat exchanger 10 for co-generation of power. The integrationof these separate processes enabled by the inventive chemicalmanufacturing process has significant benefits with respect to bothimproved economy of operation and substantially reduced environmentalimpact achieved by recycle of both energy and chemical waste streams.

Chlorine from the electrolytic cell 16 is used to chlorinate titaniumore (rutile, anatase or ilmenite) in the chlorinator 17. In thechlorination stage, the titanium ore is blended with coke and chemicallyconverted in the presence of chlorine in a fluidized-bed or othersuitable kiln chlorinator. The titanium dioxide contained in the rawmaterial reacts to form titanium tetrachloride, while the oxygen formscarbon dioxide with the coke. Iron and other impurity metals present inthe ore are also converted during chlorination to their correspondingchlorides. The titanium chloride is then condensed and purified by meansof distillation in column 18. With current practice, the purifiedtitanium chloride vapor would be condensed again and sold to titaniummanufacturers; however, in this integrated process, the titaniumtetrachloride vapor stream is used directly in the manufacturing processvia a feed pump 21 and boiler 22.

After providing process heat for the distillation step in heatexchangers 19 and 20, the temperature of the bulk process stream isadjusted to the desired temperature for the reaction chamber 14 at heatexchanger 10, and then combined with the regenerated sodium recyclestream, and injected into the reaction chamber. The recovered heat fromheat exchangers 19 and 20 may be used to vaporize liquid halide from thesource thereof to produce halide vapor to react with the metal or thenon-metal. It should be understood that various pumps, filters, traps,monitors and the like will be added as needed by those skilled in theart.

In all aspects, for the process of FIG. 1, it is important that thetitanium that is removed from the separator 15 be at or below thesintering temperature of titanium in order to preclude and prevent thesolidification of the titanium on the surfaces of the equipment and theagglomeration of titanium particles into large masses, which is one ofthe fundamental difficulties with the commercial processes usedpresently. By maintaining the temperature of the titanium metal belowthe sintering temperature of titanium metal, the titanium will notattach to the walls of the equipment or itself as it occurs with priorart and, therefore, the physical removal of the same will be obviated.This is an important aspect of this invention and is obtained by the useof sufficient sodium metal or diluent gas or both to control thetemperature of the elemental (or alloy) product. In other aspects, FIG.1, is illustrative of the types of design parameters which may be usedto produce titanium metal in a continuous process which avoids theproblems with the prior art. Referring now to FIG. 2, there is discloseda typical reaction chamber in which a choke flow or injection nozzle 23,completely submerged in a flowing liquid metal stream, introduces thehalide vapor from a boiler 22 in a controlled manner into the liquidmetal reductant stream 13. The reaction process is controlled throughthe use of a choke-flow (sonic or critical flow) nozzle. A choke-flownozzle is a vapor injection nozzle that achieves sonic velocity of thevapor at the nozzle throat. That is the velocity of the vapor is equalto the speed of sound in the vapor medium at the prevailing temperatureand pressure of the vapor at the nozzle throat. When sonic conditionsare achieved, any change in downstream conditions that causes a pressurechange cannot propagate upstream to affect the discharge. The downstreampressure may then be reduced indefinitely without increasing ordecreasing the discharge. Under choke flow conditions only the upstreamconditions need to be controlled to control the flow-rate. The minimumupstream pressure required for choke flow is proportioned to thedownstream pressure and termed the critical pressure ratio. This ratiomay be calculated by standard methods.

The choke flow nozzle serves two purposes: (1) it isolates the vaporgenerator from the liquid metal system, precluding the possibility ofliquid metal backing up in the halide feed system and causingpotentially dangerous contact with the liquid halide feedstock, and (2)it delivers the vapor at a fixed rate, independent of temperature andpressure fluctuations in the reaction zone, allowing easy and absolutecontrol of the reaction kinetics.

The liquid metal stream also has multiple functional uses: (1) itrapidly chills the reaction products, forming product powder withoutsintering, (2) it transports the chilled reaction products to aseparator, (3) it serves as a heat transfer medium allowing usefulrecovery of the considerable reaction heat, and (4) it feeds one of thereactants to the reaction zone.

For instance in FIG. 2, the sodium 13 entering the reaction chamber isat 200° C. having a flow rate of 38.4 kilograms per minute. The titaniumtetrachloride from the boiler 22 is at 2 atmospheres and at atemperature of 164° C., the flow rate through the line was 1.1 kg/min.Higher pressures may be used, but it is important that back flow beprevented, so the minimum pressure should be above that determined bythe critical pressure ratio for sonic conditions, or about two times theabsolute pressure of the sodium stream (two atmospheres if the sodium isat atmospheric pressure) is preferred to ensure that flow through thereaction chamber nozzle is critical or choked.

The batch process illustrated in FIG. 3 shows a subsurface introductionof titanium tetrachloride vapor through an injection or an injector or achoke flow nozzle 23 submerged in liquid sodium contained in a reactionvessel 24. The halide vapor from the boiler 22 is injected in acontrolled manner where it reacts producing titanium powder and sodiumchloride. The reaction products fall to the bottom of the tank 25 wherethey are collected for removal. The tank walls are cooled via coolingcolis 24 and a portion of the sodium in the tank is pumped out via pump11 and recycled through a heat exchanger 10 and line 5 back to the tankto control the temperature of the sodium in the reaction vessel. Processtemperatures and pressures are similar to the continuous flow case withbulk sodium temperature of 200° C., titanium tetrachloride vapor of 164°C., and the feed pressure of the titanium tetrachloride vapor abouttwice the pressure in the reaction vessel.

In the flow diagrams of FIGS. 1 and 3, sodium make-up is indicated bythe line 13 and this may come from an electrolytic cell 16 or some otherentirely different source of sodium. In other aspects, FIG. 3 isillustrative of the types of design parameters which may be used toproduce titanium metal in a batch process which avoids agglomerationproblems inherent in the batch process presently in use commercially.

Brief Description of the Production of Titanium

FIG. 4 shows a schematic depiction of a loop used to produce titaniummetal powder. The parts of the loop of most importance to the operationare a large (10 liter) reaction vessel 29 with a collection funnel 28 atthe bottom feeding into a recycle stream. The recycle stream has a lowvolume, low head, electromagnetic pump 11 and a flow meter 25.

A titanium tetrachloride injection system consisted of a heated transferline, leading from a heated tank 30 with a large heat capacity, to asubmerged choke flow nozzle 23. The system could be removed completelyfrom the sodium loop for filling and cleaning. It should be understoodthat some commercial grades of Na have Ca or other alkaline earth metalstherein. This has no substantial affect on the invention.

Operation

A typical operating procedure follows:

-   -   1. Raise temperature of sodium loop to desired point (200° C.).    -   2. Open titanium tetrachloride tank and fill with titanium        tetrachloride.    -   3. Insert the nozzle into the airlock above the ball valve 33.    -   4. Heat titanium tetrachloride tank to desired temperature (168°        C.) as determined by vapor pressure curve (2 atm.) and the        required critical flow pressure.    -   5. Start an argon purge through the nozzle.    -   6. Open ball valve 33 and lower the nozzle into sodium.    -   7. Stop the purge and open valve 32 allowing titanium        tetrachloride to flow through the nozzle into the sodium.    -   8. When titanium tetrachloride pressure drops close to the        critical pressure ratio, close the valve 32 and withdraw the        nozzle above valve 33.    -   9. Close valve 33 and let the nozzle cool to room temperature.    -   10. Remove the titanium tetrachloride delivery system and clean.

The injection of titanium tetrachloride was monitored by measuring thepressure in the titanium tetrachloride system. A pressure transducer 31was installed and a continuous measurement of pressure was recorded on astrip chart.

A filtration scheme was used to remove products from the bulk sodium atthe end of the test. The recycle stream system was removed from thesodium loop. In its place, a filter 26 consisting of two 5 cm diameterscreens with 100 μm holes in a housing 20 cm long, was plumbed into adirect line connecting the outlet of the reaction vessel to the sodiumreceiver tank. All of the sodium was transferred to the transfer tank27.

The reaction product was washed with ethyl alcohol to remove residualsodium and then passivated with an oxygen containing gas and washed withwater to remove the sodium chloride by-product. Particle size of thesubstantially pure titanium ranged between about 0.1 and about 10 μmwith a mean size of about 5.5 μm. The titanium powder produced in theapparatus was readily separable from the sodium and sodium chlorideby-product.

The invention has been illustrated by reference to titanium alone andtitanium tetrachloride as a feedstock, in combination with sodium as thereducing metal. However, it should be understood that the foregoing wasfor illustrative purposes only and the invention clearly pertains tothose metals and non-metals in Table 1, which of course include thefluorides of uranium and rhenium and well as other halides such asbromides. Moreover, sodium while being the preferred reducing metalbecause of cost and availability, is clearly not the only availablereductant. Lithium, potassium as well as magnesium, calcium and otheralkaline earth metals are available and thermodynamically feasible.Moreover, combinations of alkali metals and alkaline earth metals havebeen used, such as Na and Ca. The two most common reducing agents forthe production of Ti are Na and Mg, so mixtures of these two metals maybe used, along with Ca, which is present in some Na as a by product ofthe method of producing Na. It is well within the skill of the art todetermine from the thermodynamic Tables which metals are capable ofacting as a reducing agent in the foregoing reactions, the principalapplications of the process being to those illustrated in Table 1 whenthe chloride or halide is reduced to the metal. Moreover, it is wellwithin the skill of the art and it is contemplated in this inventionthat alloys can be made by the process of the subject invention byproviding a suitable halide feed in the molecular ratio of the desiredalloy.

In the process described in the '761 patent, FIG. 2 and the descriptionthereof as well as in the '106 patent, FIG. 2 and the descriptionthereof as well as in FIG. 2 and the description thereof in the parentapplication Ser. No. 09/264,877, there is inherently produced Ti powderand Ti alloy powder having unique properties. More particularly, the Tiinherently produced has an iron concentration of less than 200 ppm asmeasured by ICPQ; a nitrogen concentration of less than 200 ppm, and ahydrogen concentration of less than about 100 ppm as measured by a LECOgas analyzer. The Ti powder inherently produced by the process mentionedin this paragraph is encrusted with NaCl, when formed, but whenthoroughly washed to remove the NaCl, the remaining Ti powder has achlorine concentration of less than 100 ppm as measured by neutronactivation analysis.

Moreover, the Ti powder inherently produced after washing and separationhas a packing fraction of between about 4% to about 11% as determined bya tap density measurements in which the Ti powder is introduced into agraduated test tube and tapped until the powder is fully settled.Thereafter, the weight of the powder is measured and the packingfraction or percent of theoretical density is calculated.

In addition, the Ti powder inherently produced has a BET surface arearanging from 0.4 m²/gm for a sample of the largest particles to about6.4 m²/gm for a sample of the smallest particles or fines. With finesseparated from the material, the BET surface area for samples is in therange of about 0.4 to about 1.0 m²/gm. Calculation of the particlediameters based on the BET surface area and assuming spherical shaperesults in particle diameters in the range of from about 3.3 to about1.3 microns when the fines have been removed. By separation of fines, wemean that a sample of particles produced by the inventive method whichdo not readily settle in minutes are classified as fines. During theproduction of the Ti powder by the inventive method both agglomeratedparticles and unagglomerated particles are inherently produced. Forinstance, when the Na temperature after the reaction downstream of thetip of nozzle 23 is near 350° C., the agglomerates are small on averageabout 0.2 mm in any one direction, whereas when the Na temperature afterthe reaction downstream of the top of nozzle 23 is higher, for instanceabout 450° C., the agglomerates are larger, on average of about 1.6 mmin any one direction.

Prior art Ti powder has been made by one of two processes, either ahydride/dehydride process which produced flake shaped powder or aprocess in which Ti is melted followed by atomization which results inspherical shaped powders. Low quality (high impurity) fines are producedin the Hunter process. The Ti and Ti alloy powder inherently made by theprocess disclosed herein is neither flake-shaped nor spherical shaped,as defined in Powder Metallurgy Science, by Randall M. German, secondedition, ©Metal Powder Industries Federation 1984, 1994 page 63, astandard reference book. Morphology as used herein includes powder shapeand size. The morphology of the powder illustrated in FIG. 5 is unlikeany Ti powder known to the applicants, including Hunter fines. Withreference to FIG. 5, the large shiny globes and crystals are NaCl, notthe titanium produced according to the method of the '761 and '106patents. FIG. 6 is another SEM of Ti powder made in accordance with theprocess set forth in the '761 and '106 patents, also at 3000magnification as is FIG. 5.

FIGS. 7 and 8 are SEMs of Ti alloy made in accordance with the processof the '761 and '106 patents; however, these SEMs are at 5000 and at10,000 magnification, respectively. These SEMs (5-8) are differentmorphologically with respect to the powders made and distilled as taughtin U.S. Pat. No. 6,409,797 using distillation to separate excess Na fromthe reaction products and morphologically different from other Tipowders known to applicants.

It has been well known in the powder metallurgy art prior to Aug. 1,1994, how to convert metal powder to solid shapes by a variety ofprocesses, such as powder metallurgy using press and sinter methods,powder injection molding, metal injection molding, powder to plate,continuous casting techniques by way of example, only. These well knownmethods, prior to Aug. 1, 1994, had been used to convert titanium powderto solid product as well as a wide variety of other metals and metalalloy powders.

While there has been disclosed what is considered to be the preferredembodiment of the present invention, it is understood that variouschanges in the details may be made without departing from the spirit, orsacrificing any of the advantages of the present invention.

1-48. (canceled)
 49. A titanium powder produced by introducing a TiCl₄vapor into a flowing stream of sodium alkali metal at a velocity notless than sonic velocity of the vapor wherein the sodium is present inan amount greater than stoichiometric sufficient to maintainsubstantially all the reaction products below the sintering temperaturethereof and, wherein said Ti powder has a packing fraction in the rangeof from about 4% to about 11%. 50-83. (canceled)
 84. A titanium ortitanium alloy powder produced by the method of submerging a titaniumhalide vapor or mixture of halide vapors in a continuum of liquid sodiummetal thereof present in sufficient quantities to maintain the titaniumor titanium alloy below the sintering temperatures thereof wherein thepowder is titanium without fines and has a particle diameter in therange of from about 3.3 to about 1.3 microns based on a calculated sizeof a sphere from a BET surface area in the range of from about 0.4 toabout 1.0 m²/g, and, wherein said Ti powder has a packing fraction inthe range of from about 4% to about 11%. 95-99. (canceled)